US20160200747A1 - Phosphorus-containing compound and curing epoxy resin composition containing same - Google Patents

Phosphorus-containing compound and curing epoxy resin composition containing same Download PDF

Info

Publication number
US20160200747A1
US20160200747A1 US14/915,766 US201414915766A US2016200747A1 US 20160200747 A1 US20160200747 A1 US 20160200747A1 US 201414915766 A US201414915766 A US 201414915766A US 2016200747 A1 US2016200747 A1 US 2016200747A1
Authority
US
United States
Prior art keywords
group
phosphorus
containing compound
epoxy resin
alkyl group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US14/915,766
Other versions
US9738667B2 (en
Inventor
Takeshi Endo
Kozo Matsumoto
Ken-ichi TAMASO
Ryo Ogawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Adeka Corp
Original Assignee
Adeka Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Adeka Corp filed Critical Adeka Corp
Assigned to ADEKA CORPORATION reassignment ADEKA CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ENDO, TAKESHI, MATSUMOTO, KOZO, OGAWA, RYO, TAMASO, KEN-ICHI
Publication of US20160200747A1 publication Critical patent/US20160200747A1/en
Application granted granted Critical
Publication of US9738667B2 publication Critical patent/US9738667B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/242—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/224—Phosphorus triamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/44—Amides
    • C08G59/446—Phosphoramides

Definitions

  • This invention relates to a phosphorus-containing compound, particularly a reactive phosphorus-containing compound that can be combined with an epoxy compound to provide a curing epoxy resin composition expected to achieve flame retardation, reduction of dielectric constant, and the like.
  • Patent Document 1 proposes adding a phosphorus-containing flame retardant composed of a high-molecular-weight divalent phenol and a phenol to an epoxy resin. Nevertheless, the proposed flame retardant should be used in a large quantity in order to impart sufficient flame retardancy to an epoxy resin. Adding a sufficient amount of the flame retardant to realize satisfactory flame retardation causes reduction in glass transition temperature, and reduction in amount of the flame retardant to be added in an attempt to increase the glass transition temperature results in insufficient flame retardancy.
  • Patent Document 2 proposes using a reactive phosphoric ester compound.
  • An object of the invention is to provide a phosphorus-containing compound having reactivity with a glycidyl group, particularly a phosphorus-containing compound having glycidyl reactivity and therefore capable of providing a curing epoxy resin composition that is expected to achieve flame retardation, reduction of dielectric constant, and the like.
  • the invention provides a phosphorus-containing compound represented by general formula (I):
  • R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, or an aryl group
  • R 5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group
  • X represents an oxygen atom or a sulfur atom
  • Y represents an oxygen atom, a sulfur atom, or ⁇ NR′
  • R′ represents a hydrogen atom, an alkyl group, or an aryl group.
  • the invention also provides a reaction process comprising causing the above-described phosphorus-containing compound to react with an epoxy compound according to the following reaction scheme:
  • R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, or an aryl group
  • R 5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group
  • X represents an oxygen atom or a sulfur atom
  • Y represents an oxygen atom, a sulfur atom, or ⁇ NR 6
  • R 6 represents a hydrogen atom, an alkyl group, or an aryl group
  • Ar represents an aromatic group.
  • the invention also provides an epoxy resin curing agent containing the above described phosphorus-containing compound.
  • the invention also provides a curing epoxy resin composition containing the epoxy resin curing agent.
  • the invention provides a phosphorus-containing compound having excellent reactivity with an epoxy resin and promising to impart flame retardation to the epoxy resin and to reduce the dielectric constant of the epoxy resin.
  • FIG. 1 is a 1 H-NMR spectrum of the phosphorus-containing compound (I-1) obtained in Example 1.
  • FIG. 2 is a 31 P-NMR spectrum of the phosphorus-containing compound (I-1) obtained in Example 1.
  • FIG. 3 is a GC-MS spectrum of the phosphorus-containing compound (I-1) obtained in Example 1.
  • FIG. 4 is a 1 H-NMR spectrum of the phosphorus-containing compound (I-2) obtained in Example 2.
  • FIG. 5 is a 31 P-NMR spectrum of the phosphorus-containing compound (I-2) obtained in Example 2.
  • FIG. 6 is a GC-MS spectrum of the phosphorus-containing compound (I-2) obtained in Example 2.
  • FIG. 7 is a 1 H-NMR spectrum of the phosphorus-containing compound (I-3) obtained in Example 3.
  • FIG. 8 is a 31 P-NMR spectrum of the phosphorus-containing compound (I-3) obtained in Example 3.
  • FIG. 9 is a GC-MS spectrum of the phosphorus-containing compound (1-3 obtained in Example 3.
  • FIG. 10 is a 1 H-NMR spectrum of the phosphorus-containing compound (I-9) obtained in Example 4.
  • FIG. 11 is a 31 P-NMR spectrum of the phosphorus-containing compound (I-9) obtained in Example 4.
  • FIG. 12 is a 1 H-NMR spectrum of S 4 obtained in Example 5.
  • FIG. 13 is a 31 P-NMR spectrum of S 4 obtained in Example 5.
  • FIG. 14 is a GC-MS spectrum of S 4 obtained in Example 5.
  • FIG. 15 is a 1 H-NMR spectrum of S 5 obtained in Example 6.
  • FIG. 16 is a 31 P-NMR spectrum of S 5 obtained in Example 6.
  • FIG. 17 is a GC-MS spectrum of S 5 obtained in Example 6.
  • the invention will be described based on its preferred embodiments.
  • the phosphorus-containing compound according to the invention is a novel compound represented by general formula (I) and has a reactive group with a glycidyl group in its structure.
  • Examples of the alkyl group as represented by R 1 , R 2 , R 3 , R 4 , and R′ (when Y is ⁇ NR′) in general formula (I) include those having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, isohexyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, and decyl.
  • Examples of the aryl group as represented by R 1 , R 2 , R 3 , R 4 , and R′ include those having 6 to 12 carbon atoms, such as phenyl and naphthyl.
  • R 1 , R 2 , R 3 , and R 4 are each preferably an alkyl group having 1 to 5 carbon atoms.
  • Examples of the alkyl group as represented by R 5 include those having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, isohexyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, and decyl.
  • Examples of the alkanediyl group as R 5 include those having 1 to 10 carbon atoms, such as methylene, ethylene, propylene, butylene, and octylene.
  • alkanetriyl group as R 5 examples include those having 1 to 6 carbon atoms, such as methylenetriyl and 1,1,3-ethylenetriyl.
  • the alkanetetrayl as R 5 is exemplified by those having 2 to 6 carbon atoms, such as 1,1,2,2-ethylenetriyl.
  • Examples of the aromatic group as represented by R 5 include those derived from mononuclear polyhydric phenol compounds, such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol, and those derived from polynuclear polyhydric phenol compounds, such as dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(o-cresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolak, o-cre
  • n an integer of 1 to 4,
  • R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; o represents an integer of 1 to 3; p represents an integer of 0 to 50;
  • R 1 , R 2 , R 3 , R 4 , X, and Y are as defined above;
  • R 7 represents
  • R 8 and R 9 each represent a hydrogen atom, CH 3 , or CF 3 ,
  • t represents an integer of 4 to 12
  • R 10 represents a hydrogen atom or CH 3 ; and R 1 , R 2 , R 3 , R 4 , X, and Y are as defined above,
  • r represents an integer of 0 to 25, and s represents an integer of 0 to 25, provided that the sum of r and s is 5 to 50; and Z is as defined above.
  • phosphorus-containing compound of the invention include those represented by formulae (I-1) through (I-9):
  • phosphorus-containing compounds of the invention preferred are those of general formula (I) in which R 1 , R 2 , R 3 , and R 4 each independently represent a C1-C5 alkyl group; R 5 represents the aromatic group represented by the formulae (1) to (9); and X and Y are each oxygen in terms of phosphorus content and ready availability of starting materials used to synthesize the compound.
  • the phosphorus-containing compound of the invention can be prepared by a method shown by the following reaction scheme (A) or (B):
  • R 1 , R 2 , R 3 , R 4 , R 5 , X, and Y are as defined above.
  • R 1 , R 2 , R 3 , R 4 , R 5 , X, and Y are as defined above.
  • Examples of the base that can be used in the above reactions include tertiary amines, such as triethylamine, tributylamine, diazabicycloundecene, diazabicyclononene, and 1,4-diazabicyclo[2.2.2]octane; pyridines, such as pyridine and N,N-dimethylaminopyridine; imidazoles, such as 1-methylimidazole; and phosphines, such as triphenylphosphine, tributylphosphine, and tricyclohexylphosphine.
  • tertiary amines such as triethylamine, tributylamine, diazabicycloundecene, diazabicyclononene, and 1,4-diazabicyclo[2.2.2]octane
  • pyridines such as pyridine and N,N-dimethylaminopyridine
  • Examples of the solvent that can be used in the above reactions include ketones, such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexanone; ethers, such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and propylene glycol monomethyl ether; esters, such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons, such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons, such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; and halogenated aromatic hydrocarbons, such as chlorobenzene.
  • ketones such as methyl ethyl ketone, methyl
  • the reactions shown above are carried out at a temperature of ⁇ 80° to 100° C., preferably room temperature to 50° C., for a period of 0.5 to 72 hours, preferably 1 to 24 hours.
  • the phosphorus-containing compound of the invention efficiently reacts with an epoxy compound according to the following reaction scheme and is suitably used as an epoxy resin curing agent.
  • R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an alkyl group, or an aryl group
  • R 5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group
  • X represents an oxygen atom or a sulfur atom
  • Y represents an oxygen atom, a sulfur atom, or ⁇ NR 6
  • R 6 represents a hydrogen atom, an alkyl group, or an aryl group
  • Ar represents an aromatic group.
  • Examples of the aromatic group as represented by Ar in the above reaction formula include the aryl groups as represented by R 1 and so on and the aromatic groups as represented by R 5 as described with reference to the general formula (I).
  • the epoxy resin curing agent of the invention comprises at least one of the phosphorus-containing compounds of the invention. That is, the phosphorus-containing compounds of the invention can be used as an epoxy resin curing agent either individually or in combination with one another.
  • the epoxy resin curing agent of the invention may comprise known epoxy resin curing agents in addition to the phosphorus-containing compound of the invention.
  • Useful known epoxy resin curing agents include general-purpose epoxy resin curing agents that will hereinafter be described for use in the curing epoxy resin composition of the invention.
  • the known epoxy resin curing agents may be used as a mixture of two or more thereof.
  • the content of the phosphorus-containing compound of the invention in the epoxy resin curing agent of the invention is preferably 5% to 100% by mass, more preferably 20% to 100% by mass.
  • the curing epoxy resin composition according to the invention comprises an epoxy compound (epoxy resin) and the epoxy resin curing agent containing the phosphorus-containing compound of the invention.
  • Examples of the epoxy compound that can be used in the curing epoxy resin composition of the invention include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds, such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; polyglycidyl ether compounds of polynuclear polyhydric phenol compounds, such as dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(o-cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfon
  • epoxy compounds may be internally crosslinked by a prepolymer of the terminal isocyanate or may have their molecular weight increased by a polyvalent active hydrogen compound (e.g., polyhydric phenols, polyamines, carbonyl-containing compounds, and polyphosphoric esters).
  • a polyvalent active hydrogen compound e.g., polyhydric phenols, polyamines, carbonyl-containing compounds, and polyphosphoric esters.
  • the epoxy compound preferably has an epoxy equivalent of from 70 to 3,000, more preferably 90 to 2,000. With an epoxy equivalent less than 70, the physical properties of the cured product can reduce. With an epoxy equivalent larger than 3,000, curability can be insufficient.
  • the curing epoxy resin composition preferably contains 0.1 to 5 equivalents, more preferably 1 to 3 equivalents, of the epoxy compound per equivalent of the phosphorus-containing compound of the invention.
  • the curing epoxy resin composition of the invention is preferably combined with a curing catalyst, such as p-dimethylaminopyridine, triphenylphosphine, imidazole, tertiary amines, phosphines, quaternary ammonium salts, and quaternary phosphonium salts.
  • a curing catalyst such as p-dimethylaminopyridine, triphenylphosphine, imidazole, tertiary amines, phosphines, quaternary ammonium salts, and quaternary phosphonium salts.
  • the curing epoxy resin composition of the invention is preferably combined with a general-purpose epoxy resin curing agent.
  • Suitable epoxy resin curing agents include imidazoles, such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and 1-(2-methylimidazol-1-ylmethyl)naphthalen-2-ol; polyalkylpolyamines, such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; alicyclic polyamines, such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophoronediamine; and aromatic polyamines, such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenyl sulfone.
  • polyepoxy adducts of these polyamines obtained by the reaction with various epoxy resins such as glycidyl ethers (e.g., phenyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, and bisphenol F glycidyl ether) or carboxylic acid glycidyl esters in a usual manner; amide-modified products of the organic polyamines obtained by the reaction with carboxylic acids (e.g., phthalic acid, isophthalic acid, and dimer acid) in a usual manner; and Mannich-modified products of the polyamines obtained by the reaction with aldehydes (e.g., formaldehyde) and phenols having at least one aldehyde-reactive site on their nucleus (e.g., phenol, cresol, xylenol, tert-butylphenol, and resorcinol) in
  • the curing epoxy resin composition of the invention may contain commonly used additives, including reactive or nonreactive diluents (plasticizers), such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar; fillers or pigments, such as glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black, graphite, iron oxide, and bituminous materials; silane coupling agents, such as ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)-N′ ⁇ -(aminoethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -a
  • the curing epoxy resin composition of the invention can be used for a wide range of applications, such as coatings or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastics, wood, cloth, and paper; pressure-sensitive adhesives for packaging adhesive tape, adhesive labels, labels for frozen foods, removable labels, labels for POS system, adhesive wallpaper, and adhesive flooring; processed paper, such as art paper, light-weight coated paper, cast-coated paper, coated paperboard, carbonless copy paper, and impregnated paper; textile processing agents, such as sizing agents, anti-fray agents, and processing agents for natural fibers, synthetic fibers, glass fiber, carbon fiber, and metal fibers; building materials, such as sealants, cement admixtures, and waterproof materials; and sealants for electronic/electric devices.
  • applications such as coatings or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastics, wood, cloth, and paper; pressure-sensitive adhesives for packaging adhesive tape, adhesive labels, labels for frozen foods, removable labels, labels for POS system, adhesive
  • a 100 ml three-necked flask equipped with a rotor, a reflux tube, and a rubber septum was charged with 0.1 g (1 mmol) of 4-dimethylaminopyridine (DMAP). After thoroughly drying and purging with nitrogen, the flask was charged with 0.9 g (10 mmol) of phenol and 10 ml of ultra-dehydrated tetrahydrofuran using a syringe. To the mixture was added dropwise 2.0 g (12 mmol) of bis(dimethylamino)phosphoryl chloride using a syringe taking care so that the reaction temperature did not exceed 30° C. After completion of the addition, the reaction system was stirred for 10 minutes.
  • DMAP 4-dimethylaminopyridine
  • the intermediate product was dissolved in 10 ml of dehydrated tetrahydrofuran to prepare a THF solution of the intermediate product. Then, a 100 ml three-necked flask equipped with a rotor, a reflux tube, and a rubber septum was thoroughly dried, purged with nitrogen, and charged with 18.08 g (42 mmol) of a methylamine tetrahydrofuran solution and 4.25 g (42 mmol) of triethylamine while cooling in a salt-ice-water bath. After stirring for 5 minutes, the THF solution of the intermediate product was added thereto dropwise using a syringe taking care not to let the reaction temperature exceed 20° C. After the addition, the stirring was continued for 1 hour.
  • Adeka Resin EP-4100L weighing 1.02 g (100.0 phr), 0.16 g (15.7 phr) of the phosphorus-containing compound [I-9] of the invention, and 0.03 g (3.0 phr) of 2-ethyl-4-methylimidazole were mixed and heated in a thermostat at 150° C. for 3 hours and then at 180° C. for 3 hours to give a tack-free, brown cured product.
  • the Tg of the cured product was found to be 140° C. as a result of DSC.
  • Examples of the invention proved that the phosphorus-containing compounds of the invention have reactivity with a glycidyl group.
  • Compounding the phosphoric ester of the invention into an epoxy resin composition provides an epoxy resin cured product that is expected to have flame retardancy and a reduced dielectric constant without causing reduction in physical properties of the cured product.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)

Abstract

Provided is a novel phosphorus-containing compound represented by general formula (I). The compound has reactivity with a glycidyl group and is therefore capable of providing a curing epoxy resin composition that is expected to achieve flame retardation and reduction of dielectric constant.
Figure US20160200747A1-20160714-C00001
wherein m is a number of 1 to 10; R1, R2, R3, and R4 are each hydrogen, alkyl, or aryl; R5 is alkyl, alkanediyl, alkanetriyl, alkanetetrayl, or an aromatic group; X is oxygen or sulfur; Y is oxygen, sulfur, or ═NR′; and R′ is hydrogen, alkyl, or aryl.

Description

    TECHNICAL FIELD
  • This invention relates to a phosphorus-containing compound, particularly a reactive phosphorus-containing compound that can be combined with an epoxy compound to provide a curing epoxy resin composition expected to achieve flame retardation, reduction of dielectric constant, and the like.
    • BACKGROUND ART
  • The recent increase in concern with a global environmental problem and safety of the human body has boosted the demand for less hazard and more safety, as well as flame retardancy, of electric/electronic products. That is, reduction of harmful gas and smoke generation has been demanded.
  • Use of a bromine-containing flame retardant, which provides good flame retardancy, has been being limited on account of generation of toxic hydrogen halide gas (hydrogen bromide) on combustion. Therefore, studies have been directed to compositions containing an ordinary epoxy resin and a halogen-free flame retardant, such as a nitrogen compound, a phosphorus compound, or an inorganic compound. However, these additives for imparting flame retardancy are disadvantageous in that their flame retardant effect is insufficient or they adversely affect curing of the epoxy resin or are accompanied by reduction of physical properties, such as a glass transition temperature, of a cured product.
  • For example, triphenyl phosphate is widely used as a phosphorous-containing flame retardant for various resins. Patent Document 1 described below proposes adding a phosphorus-containing flame retardant composed of a high-molecular-weight divalent phenol and a phenol to an epoxy resin. Nevertheless, the proposed flame retardant should be used in a large quantity in order to impart sufficient flame retardancy to an epoxy resin. Adding a sufficient amount of the flame retardant to realize satisfactory flame retardation causes reduction in glass transition temperature, and reduction in amount of the flame retardant to be added in an attempt to increase the glass transition temperature results in insufficient flame retardancy. Patent Document 2 below proposes using a reactive phosphoric ester compound. The proposal has turned out to be impractical because incorporating the phosphoric ester compound into an epoxy resin makes the resin hygroscopic or makes part of the resin take on a three-dimensional structure, which increases the viscosity and thereby greatly reduces the workability of the resin composition.
    • CITATION LIST Patent Document
    • Patent Document 1: JP 8-337709A
    • Patent Document 2: JP 10-195178A
    SUMMARY OF THE INVENTION Problem to be Solved by the Invention
  • An object of the invention is to provide a phosphorus-containing compound having reactivity with a glycidyl group, particularly a phosphorus-containing compound having glycidyl reactivity and therefore capable of providing a curing epoxy resin composition that is expected to achieve flame retardation, reduction of dielectric constant, and the like.
    • Means for Solving the Problem
  • As a result of extensive investigations, the inventors have found that a phosphorus-containing compound having a specific structure accomplishes the above object and reached the present invention.
  • The invention provides a phosphorus-containing compound represented by general formula (I):
  • Figure US20160200747A1-20160714-C00002
  • wherein m represents a number of 1 to 10; R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group, or an aryl group; R5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group; X represents an oxygen atom or a sulfur atom; Y represents an oxygen atom, a sulfur atom, or ═NR′; and R′ represents a hydrogen atom, an alkyl group, or an aryl group.
  • The invention also provides a reaction process comprising causing the above-described phosphorus-containing compound to react with an epoxy compound according to the following reaction scheme:
  • Figure US20160200747A1-20160714-C00003
  • wherein m represents a number of 1 to 10; R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group, or an aryl group; R5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group; X represents an oxygen atom or a sulfur atom; Y represents an oxygen atom, a sulfur atom, or ═NR6; R6 represents a hydrogen atom, an alkyl group, or an aryl group; and Ar represents an aromatic group.
  • The invention also provides an epoxy resin curing agent containing the above described phosphorus-containing compound.
  • The invention also provides a curing epoxy resin composition containing the epoxy resin curing agent.
    • Effect of the Invention
  • The invention provides a phosphorus-containing compound having excellent reactivity with an epoxy resin and promising to impart flame retardation to the epoxy resin and to reduce the dielectric constant of the epoxy resin.
    • BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
  • FIG. 1 is a 1H-NMR spectrum of the phosphorus-containing compound (I-1) obtained in Example 1.
  • FIG. 2 is a 31P-NMR spectrum of the phosphorus-containing compound (I-1) obtained in Example 1.
  • FIG. 3 is a GC-MS spectrum of the phosphorus-containing compound (I-1) obtained in Example 1.
  • FIG. 4 is a 1H-NMR spectrum of the phosphorus-containing compound (I-2) obtained in Example 2.
  • FIG. 5 is a 31P-NMR spectrum of the phosphorus-containing compound (I-2) obtained in Example 2.
  • FIG. 6 is a GC-MS spectrum of the phosphorus-containing compound (I-2) obtained in Example 2.
  • FIG. 7 is a 1H-NMR spectrum of the phosphorus-containing compound (I-3) obtained in Example 3.
  • FIG. 8 is a 31P-NMR spectrum of the phosphorus-containing compound (I-3) obtained in Example 3.
  • FIG. 9 is a GC-MS spectrum of the phosphorus-containing compound (1-3 obtained in Example 3.
  • FIG. 10 is a 1H-NMR spectrum of the phosphorus-containing compound (I-9) obtained in Example 4.
  • FIG. 11 is a 31P-NMR spectrum of the phosphorus-containing compound (I-9) obtained in Example 4.
  • FIG. 12 is a 1H-NMR spectrum of S4 obtained in Example 5.
  • FIG. 13 is a 31P-NMR spectrum of S4 obtained in Example 5.
  • FIG. 14 is a GC-MS spectrum of S4 obtained in Example 5.
  • FIG. 15 is a 1H-NMR spectrum of S5 obtained in Example 6.
  • FIG. 16 is a 31P-NMR spectrum of S5 obtained in Example 6.
  • FIG. 17 is a GC-MS spectrum of S5 obtained in Example 6.
    •  BEST MODE FOR CARRYING OUT THE INVENTION
  • The invention will be described based on its preferred embodiments. The phosphorus-containing compound according to the invention is a novel compound represented by general formula (I) and has a reactive group with a glycidyl group in its structure.
  • Examples of the alkyl group as represented by R1, R2, R3, R4, and R′ (when Y is ═NR′) in general formula (I) include those having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, isohexyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, and decyl. Examples of the aryl group as represented by R1, R2, R3, R4, and R′ (when Y is=NR') include those having 6 to 12 carbon atoms, such as phenyl and naphthyl. R1, R2, R3, and R4 are each preferably an alkyl group having 1 to 5 carbon atoms.
  • Examples of the alkyl group as represented by R5 include those having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, isohexyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, and decyl. Examples of the alkanediyl group as R5 include those having 1 to 10 carbon atoms, such as methylene, ethylene, propylene, butylene, and octylene. Examples of the alkanetriyl group as R5 include those having 1 to 6 carbon atoms, such as methylenetriyl and 1,1,3-ethylenetriyl. The alkanetetrayl as R5 is exemplified by those having 2 to 6 carbon atoms, such as 1,1,2,2-ethylenetriyl.
  • Examples of the aromatic group as represented by R5 include those derived from mononuclear polyhydric phenol compounds, such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol, and those derived from polynuclear polyhydric phenol compounds, such as dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(o-cresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolak, o-cresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, and terpene phenol. Preferred of them are groups represented by the formulae (1) through (9) shown below.
  • Figure US20160200747A1-20160714-C00004
  • wherein n represents an integer of 1 to 4,
  • Figure US20160200747A1-20160714-C00005
  • wherein R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; o represents an integer of 1 to 3; p represents an integer of 0 to 50;
  • Z represents
  • Figure US20160200747A1-20160714-C00006
  • wherein R1, R2, R3, R4, X, and Y are as defined above;
  • R7 represents
  • Figure US20160200747A1-20160714-C00007
  • wherein R8 and R9 each represent a hydrogen atom, CH3, or CF3,
  • Figure US20160200747A1-20160714-C00008
  • wherein t represents an integer of 4 to 12,
  • Figure US20160200747A1-20160714-C00009
  • wherein R10 represents a hydrogen atom or CH3; and R1, R2, R3, R4, X, and Y are as defined above,
  • Figure US20160200747A1-20160714-C00010
  • wherein q represents an integer of 0 to 50, and Z is as defined above, and
  • Figure US20160200747A1-20160714-C00011
  • wherein r represents an integer of 0 to 25, and s represents an integer of 0 to 25, provided that the sum of r and s is 5 to 50; and Z is as defined above.
  • Specific examples of the phosphorus-containing compound of the invention include those represented by formulae (I-1) through (I-9):
  • Figure US20160200747A1-20160714-C00012
    Figure US20160200747A1-20160714-C00013
  • Of the phosphorus-containing compounds of the invention preferred are those of general formula (I) in which R1, R2, R3, and R4 each independently represent a C1-C5 alkyl group; R5 represents the aromatic group represented by the formulae (1) to (9); and X and Y are each oxygen in terms of phosphorus content and ready availability of starting materials used to synthesize the compound.
  • The phosphorus-containing compound of the invention can be prepared by a method shown by the following reaction scheme (A) or (B):
  • Figure US20160200747A1-20160714-C00014
  • wherein R1, R2, R3, R4, R5, X, and Y are as defined above.
  • Figure US20160200747A1-20160714-C00015
  • wherein R1, R2, R3, R4, R5, X, and Y are as defined above.
  • Examples of the base that can be used in the above reactions include tertiary amines, such as triethylamine, tributylamine, diazabicycloundecene, diazabicyclononene, and 1,4-diazabicyclo[2.2.2]octane; pyridines, such as pyridine and N,N-dimethylaminopyridine; imidazoles, such as 1-methylimidazole; and phosphines, such as triphenylphosphine, tributylphosphine, and tricyclohexylphosphine.
  • Examples of the solvent that can be used in the above reactions include ketones, such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexanone; ethers, such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and propylene glycol monomethyl ether; esters, such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons, such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons, such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; and halogenated aromatic hydrocarbons, such as chlorobenzene.
  • The reactions shown above are carried out at a temperature of −80° to 100° C., preferably room temperature to 50° C., for a period of 0.5 to 72 hours, preferably 1 to 24 hours.
  • The phosphorus-containing compound of the invention efficiently reacts with an epoxy compound according to the following reaction scheme and is suitably used as an epoxy resin curing agent.
  • Figure US20160200747A1-20160714-C00016
  • wherein m represents a number of 1 to 10; R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group, or an aryl group; R5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group; X represents an oxygen atom or a sulfur atom; Y represents an oxygen atom, a sulfur atom, or ═NR6; R6 represents a hydrogen atom, an alkyl group, or an aryl group; and Ar represents an aromatic group.
  • Examples of the aromatic group as represented by Ar in the above reaction formula include the aryl groups as represented by R1 and so on and the aromatic groups as represented by R5 as described with reference to the general formula (I).
  • The epoxy resin curing agent of the invention comprises at least one of the phosphorus-containing compounds of the invention. That is, the phosphorus-containing compounds of the invention can be used as an epoxy resin curing agent either individually or in combination with one another. The epoxy resin curing agent of the invention may comprise known epoxy resin curing agents in addition to the phosphorus-containing compound of the invention. Useful known epoxy resin curing agents include general-purpose epoxy resin curing agents that will hereinafter be described for use in the curing epoxy resin composition of the invention. The known epoxy resin curing agents may be used as a mixture of two or more thereof.
  • The content of the phosphorus-containing compound of the invention in the epoxy resin curing agent of the invention is preferably 5% to 100% by mass, more preferably 20% to 100% by mass.
  • The curing epoxy resin composition according to the invention comprises an epoxy compound (epoxy resin) and the epoxy resin curing agent containing the phosphorus-containing compound of the invention.
  • Examples of the epoxy compound that can be used in the curing epoxy resin composition of the invention include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds, such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; polyglycidyl ether compounds of polynuclear polyhydric phenol compounds, such as dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(o-cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenol novolak, o-cresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, and terpene phenol; polyglycidyl ethers of polyhydric alcohols, such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, thiodiglycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-ethylene oxide adduct; homopolymers or copolymers of glycidyl methacrylate or a glycidyl ester of an aliphatic, aromatic or alicyclic polybasic acid, such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, or endomethylene tetrahydrophthalic acid; epoxy compounds having a glycidylamino group, such as N, N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidyl o-toluidine; epoxidized cyclic olefin compounds, such as vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexane carboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers, such as epoxidized polybutadiene and an epoxidized styrene-butadiene copolymer; and heterocyclic compounds, such as triglycidyl isocyanurate. These epoxy compounds may be internally crosslinked by a prepolymer of the terminal isocyanate or may have their molecular weight increased by a polyvalent active hydrogen compound (e.g., polyhydric phenols, polyamines, carbonyl-containing compounds, and polyphosphoric esters).
  • The epoxy compound preferably has an epoxy equivalent of from 70 to 3,000, more preferably 90 to 2,000. With an epoxy equivalent less than 70, the physical properties of the cured product can reduce. With an epoxy equivalent larger than 3,000, curability can be insufficient.
  • The curing epoxy resin composition preferably contains 0.1 to 5 equivalents, more preferably 1 to 3 equivalents, of the epoxy compound per equivalent of the phosphorus-containing compound of the invention.
  • The curing epoxy resin composition of the invention is preferably combined with a curing catalyst, such as p-dimethylaminopyridine, triphenylphosphine, imidazole, tertiary amines, phosphines, quaternary ammonium salts, and quaternary phosphonium salts.
  • The curing epoxy resin composition of the invention is preferably combined with a general-purpose epoxy resin curing agent. Suitable epoxy resin curing agents include imidazoles, such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and 1-(2-methylimidazol-1-ylmethyl)naphthalen-2-ol; polyalkylpolyamines, such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; alicyclic polyamines, such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophoronediamine; and aromatic polyamines, such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenyl sulfone. Further included are polyepoxy adducts of these polyamines obtained by the reaction with various epoxy resins, such as glycidyl ethers (e.g., phenyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, and bisphenol F glycidyl ether) or carboxylic acid glycidyl esters in a usual manner; amide-modified products of the organic polyamines obtained by the reaction with carboxylic acids (e.g., phthalic acid, isophthalic acid, and dimer acid) in a usual manner; and Mannich-modified products of the polyamines obtained by the reaction with aldehydes (e.g., formaldehyde) and phenols having at least one aldehyde-reactive site on their nucleus (e.g., phenol, cresol, xylenol, tert-butylphenol, and resorcinol) in a usual manner. Furthermore, latent curing agents, such as dicyandiamides, acid anhydrides, and imidazoles, are also useful.
  • If necessary, the curing epoxy resin composition of the invention may contain commonly used additives, including reactive or nonreactive diluents (plasticizers), such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar; fillers or pigments, such as glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black, graphite, iron oxide, and bituminous materials; silane coupling agents, such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-N′β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyl triethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxy silane, and γ-mercaptopropyltrimethoxysilane; lubricants, such as candelilla wax, carnauba wax, Japan wax, insect wax, beeswax, lanolin, spermaceti wax, montan wax, petroleum wax, aliphatic wax, aliphatic esters, aliphatic ethers, aromatic esters, and aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; UV absorbers; flame retardants; defoamers; rust inhibitors; colloidal silica, and colloidal alumina. Adhesive resins, such as xylene resin and petroleum resins, may be used in combination.
  • The curing epoxy resin composition of the invention can be used for a wide range of applications, such as coatings or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastics, wood, cloth, and paper; pressure-sensitive adhesives for packaging adhesive tape, adhesive labels, labels for frozen foods, removable labels, labels for POS system, adhesive wallpaper, and adhesive flooring; processed paper, such as art paper, light-weight coated paper, cast-coated paper, coated paperboard, carbonless copy paper, and impregnated paper; textile processing agents, such as sizing agents, anti-fray agents, and processing agents for natural fibers, synthetic fibers, glass fiber, carbon fiber, and metal fibers; building materials, such as sealants, cement admixtures, and waterproof materials; and sealants for electronic/electric devices.
    • EXAMPLES
  • The invention will now be illustrated in greater detail, but it should be understood that the invention is not deemed to be limited thereto.
    • Example 1 Synthesis of Phosphorus-Containing Compound [I-1]
  • A 100 ml three-necked flask equipped with a rotor, a reflux tube, and a rubber septum was charged with 0.1 g (1 mmol) of 4-dimethylaminopyridine (DMAP). After thoroughly drying and purging with nitrogen, the flask was charged with 0.9 g (10 mmol) of phenol and 10 ml of ultra-dehydrated tetrahydrofuran using a syringe. To the mixture was added dropwise 2.0 g (12 mmol) of bis(dimethylamino)phosphoryl chloride using a syringe taking care so that the reaction temperature did not exceed 30° C. After completion of the addition, the reaction system was stirred for 10 minutes. To the reaction solution were added 1.2 g (12 mmol) of triethylamine using a syringe taking care not to let the reaction temperature exceed 40° C., followed by stirring overnight. To the reaction mixture were added 5 ml of a saturated ammonium chloride aqueous solution and 5 ml of water, followed by stirring well. The solution was transferred to a separatory funnel, extracted 3 times with 10 ml portions of diethyl ether to obtain an organic layer. The organic layer was washed with 10 ml of water and dried over anhydrous magnesium sulfate. The solvent was removed using an evaporator to give pale yellow liquid (crude yield: 93.3%, GC purity: 70.5%). The crude product was purified by column chromatography (stationary phase: silica gel, mobile phase: ethyl acetate/hexane=2/1 by volume, Rf=0.20) to give the desired phosphorus-containing compound [I-1] as colorless liquid (overall yield: 44.0%, GC purity: >99%, 31P-NMR: 15.94 ppm). The results of the identification analyses are shown in FIG. 1 (1H-NMR), FIG. 2 (31P-NMR), and FIG. 3 (GC-MS).
    • Example 2 Synthesis of Phosphorus-Containing Compound [I-2]
  • A 100 ml three-necked flask equipped with a rotor, a reflux tube, and a rubber septum was thoroughly dried, purged with nitrogen, and charged with 9.5 g (21 mmol) of an ethylamine tetrahydrofuran solution, 2.1 g (21 mmol) of triethylamine, and 5 ml of ultra-dehydrated tetrahydrofuran while cooling in a salt-ice-water bath. After stirring the mixture for 5 minutes, 2.1 g (10 mmol) of phenyl dichlorophosphate was added thereto dropwise using a syringe taking care not to let the reaction temperature exceed 0° C. After completion of the addition, the reaction system was stirred for 1 hour. The salt-ice-water bath was removed, and the reaction system was stirred at room temperature overnight. To the reaction solution were added 5 ml of a saturated ammonium chloride aqueous solution and 5 ml of water, followed by stirring well. The solution was transferred to a separatory funnel, extracted 3 times with 10 ml portions of ethyl acetate to obtain an organic layer. The organic layer was washed with 10 ml of water and dried over anhydrous magnesium sulfate. The solvent was removed in an evaporator to give pale yellow liquid (crude yield: 92.9%, GC purity: 98.5%). The crude product was purified by column chromatography (stationary phase: silica gel, mobile phase: ethyl acetate, Rf=0.23) to give the desired phosphorus-containing compound [I-2] as colorless liquid (overall yield: 73.8%; GC purity: >99%, 31P-NMR: 12.01 ppm). The results of the identification analyses are shown in FIG. 4 (1H-NMR), FIG. 5 (31P-NMR), and FIG. 6 (GC-MS).
    • Example 3 Synthesis of Phosphorus-Containing Compound [I-3]
  • A 100 ml three-necked flask equipped with a rotor, a reflux tube, and a rubber septum was thoroughly dried, purged with nitrogen, and charged with 9.0 g (21 mmol) of a methylamine tetrahydrofuran solution, 2.1 g (21 mmol) of triethylamine, and 5 ml of ultra-dehydrated tetrahydrofuran while cooling in a salt-ice-water bath. After stirring the mixture for 5 minutes, 2.1 g (10 mmol) of phenyl dichlorophosphate were added thereto dropwise using a syringe taking care not to let the reaction temperature exceed 0° C. After completion of the addition, the reaction system was stirred for 1 hour. The salt-ice-water bath was removed, and the reaction system was stirred at room temperature overnight. To the reaction mixture was added 10 ml of acetone, followed by stirring well, and followed by separation into solid and filtrate by filtration. To the solid was added another 10 ml portion of acetone, followed by stirring well, and followed by separation into solid and a filtrate. The resulting solid was washed with acetone in the same manner as above. All the filtrates were collected and evaporated in an evaporator to remove the solvent thereby to give pale yellow crystals (crude yield: 110.3%, GC purity: 95.5%). The crude product was purified by column chromatography (stationary phase: silica gel, mobile phase: ethyl acetate/methanol=6/1 by volume, Rf=0.46) to give the desired phosphorus-containing compound [I-3] as white crystals (overall yield: 56.5%; GC purity: 97.4%, 31P-NMR: 15.27 ppm). The results of the identification analyses are shown in FIG. 7 (1H-NMR), FIG. 8 (31P-NMR), and FIG. 9 (GC-MS).
    • Example 4 Synthesis of Phosphorus-Containing Compound [I-9]
  • In a 30 ml two-necked flask equipped with a rotor, a reflux tube, and an inlet for introducing N2 were put 0.03 g (0.3 mmol) of magnesium chloride, 2.00 g (10 mmol) of 4,4′-methylenediphenol, and 30.67 g (200 mmol) of phosphorus oxychloride. The reaction mixture was heated until reflux while introducing N2, followed by stirring overnight at that temperature. The introduced N2 was vented from the upper end of the reflux tube and bubbled through an aqueous sodium hydroxide solution to have the by-produced hydrogen chloride trapped. After the reaction, the excess phosphorus oxychloride was removed in an evaporator to leave yellow liquid (intermediate). The intermediate product was dissolved in 10 ml of dehydrated tetrahydrofuran to prepare a THF solution of the intermediate product. Then, a 100 ml three-necked flask equipped with a rotor, a reflux tube, and a rubber septum was thoroughly dried, purged with nitrogen, and charged with 18.08 g (42 mmol) of a methylamine tetrahydrofuran solution and 4.25 g (42 mmol) of triethylamine while cooling in a salt-ice-water bath. After stirring for 5 minutes, the THF solution of the intermediate product was added thereto dropwise using a syringe taking care not to let the reaction temperature exceed 20° C. After the addition, the stirring was continued for 1 hour. The salt-ice-water bath was removed, and the reaction mixture was stirred at room temperature overnight. After completion of the reaction, the solvent and the excess of the starting material were removed in an evaporator to give pale yellow solid. The crude product was purified by column chromatography (stationary phase: silica gel, mobile phase: ethyl acetate/methanol=5/1 by volume, Rf=0.29) to yield the desired phosphorus-containing compound [I-9] as white solid (overall yield: 35.2%). The results of the identification analyses are shown in FIG. 10 (1H-NMR) and FIG. 11 (31P-NMR).
    • Example 5
  • The phosphorus-containing compound [I-2] obtained in Example 2 and weighing 57.1 mg (0.25 mmol) and 51.6 mg (0.25 mmol) of Adeka Glycirol ED-509S were allowed to react with each other in the presence of 2.3 mg (7.5 mol %) of DMAP as a catalyst in a nitrogen stream at 140° C. for 2 hours in accordance with the following reaction scheme. The results of 1H-NMR and 31P-NMR analyses shown in FIGS. 12 and 13, respectively, revealed that S4 (see below) was obtained as a main product.
  • Figure US20160200747A1-20160714-C00017
    • Example 6
  • The phosphorus-containing compound [I-3] prepared in Example 3 and weighing 50.0 mg (0.25 mmol) and 51.6 mg (0.25 mmol) of Adeka Glycirol ED-509S were allowed to react with each other in the presence of 2.3 mg (7.5 mol %) of DMAP as a catalyst in a nitrogen stream at 130° C. for 2 hours in accordance with the following reaction scheme. The results of 1H-NMR and 31P-NMR analyses shown in FIGS. 15 and 16, respectively, revealed that S5 (see below) was obtained as a main product.
  • Figure US20160200747A1-20160714-C00018
    • Example 7
  • Adeka Resin EP-4100L weighing 1.02 g (100.0 phr), 0.16 g (15.7 phr) of the phosphorus-containing compound [I-9] of the invention, and 0.03 g (3.0 phr) of 2-ethyl-4-methylimidazole were mixed and heated in a thermostat at 150° C. for 3 hours and then at 180° C. for 3 hours to give a tack-free, brown cured product. The Tg of the cured product was found to be 140° C. as a result of DSC.
  • Examples of the invention proved that the phosphorus-containing compounds of the invention have reactivity with a glycidyl group. Compounding the phosphoric ester of the invention into an epoxy resin composition provides an epoxy resin cured product that is expected to have flame retardancy and a reduced dielectric constant without causing reduction in physical properties of the cured product.

Claims (13)

1. A phosphorus-containing compound represented by general formula (I):
Figure US20160200747A1-20160714-C00019
wherein m represents a number of 1 to 10; R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group, or an aryl group; R5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group; X represents an oxygen atom or a sulfur atom; Y represents an oxygen atom, a sulfur atom, or —NR′; and R′ represents a hydrogen atom, an alkyl group, or an aryl group.
2. The phosphorus-containing compound according to claim 1, wherein the aromatic group as represented by R5 is represented by any one of formulae (1) through (9):
Figure US20160200747A1-20160714-C00020
wherein n represents an integer of 1 to 4,
Figure US20160200747A1-20160714-C00021
wherein R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; o represents an integer of 1 to 3; p represents an integer of 0 to 50;
Z represents
Figure US20160200747A1-20160714-C00022
wherein R1, R2, R3, R4, X, and Y are as defined above;
R7 represents
Figure US20160200747A1-20160714-C00023
wherein R8 and R9 each represent a hydrogen atom, CH3, or CF3,
Figure US20160200747A1-20160714-C00024
wherein t represents an integer of 4 to 12,
Figure US20160200747A1-20160714-C00025
wherein R10 represents a hydrogen atom or CH3; and R1, R2, R3, R4, X, and Y are as defined above,
Figure US20160200747A1-20160714-C00026
wherein q represents an integer of 0 to 50, and Z is as defined above, and
Figure US20160200747A1-20160714-C00027
wherein r represents an integer of 0 to 25, and s represents an integer of 0 to 25, provided that the sum of r and s is 5 to 50; and Z is as defined above.
3. The phosphorus-containing compound according to claim 1, wherein R1, R2, R3, and R4 each independently represent an alkyl group having 1 to 5 carbon atoms, R5 represents an aromatic group represented by any one of formulae (1) to (9), and X and Y each represent an oxygen atom.
4. A process comprising causing the phosphorus-containing compound according to claim 1 to react with an epoxy compound in accordance with reaction scheme:
Figure US20160200747A1-20160714-C00028
wherein m represents a number of 1 to 10; R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group, or an aryl group; R5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group; X represents an oxygen atom or a sulfur atom; Y represents an oxygen atom, a sulfur atom, or ═NR6; R6 represents a hydrogen atom, an alkyl group, or an aryl group; and Ar represents an aromatic group.
5. An epoxy resin curing agent comprising the phosphorus-containing compound according to claim 1.
6. A curing epoxy resin composition comprising the epoxy resin curing agent according to claim 5.
7. The phosphorus-containing compound according to claim 2, wherein R1, R2, R3, and R4 each independently represent an alkyl group having 1 to 5 carbon atoms, R5 represents an aromatic group represented by any one of formulae (1) to (9), and X and Y each represent an oxygen atom.
8. A process comprising causing the phosphorus-containing compound according to claim 2 to react with an epoxy compound in accordance with reaction scheme:
Figure US20160200747A1-20160714-C00029
wherein m represents a number of 1 to 10; R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group, or an aryl group; R5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group; X represents an oxygen atom or a sulfur atom; Y represents an oxygen atom, a sulfur atom, or ═NR6; R6 represents a hydrogen atom, an alkyl group, or an aryl group; and Ar represents an aromatic group.
9. A process comprising causing the phosphorus-containing compound according to claim 3 to react with an epoxy compound in accordance with reaction scheme:
Figure US20160200747A1-20160714-C00030
wherein m represents a number of 1 to 10; R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group, or an aryl group; R5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group; X represents an oxygen atom or a sulfur atom; Y represents an oxygen atom, a sulfur atom, or ═NR6; R6 represents a hydrogen atom, an alkyl group, or an aryl group; and Ar represents an aromatic group.
10. A process comprising causing the phosphorus-containing compound according to claim 7 to react with an epoxy compound in accordance with reaction scheme:
Figure US20160200747A1-20160714-C00031
wherein m represents a number of 1 to 10; R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group, or an aryl group; R5 represents an alkyl group, an alkanediyl group, an alkanetriyl group, an alkanetetrayl group, or an aromatic group; X represents an oxygen atom or a sulfur atom; Y represents an oxygen atom, a sulfur atom, or ═NR6; R6 represents a hydrogen atom, an alkyl group, or an aryl group; and Ar represents an aromatic group.
11. An epoxy resin curing agent comprising the phosphorus-containing compound according to claim 2.
12. An epoxy resin curing agent comprising the phosphorus-containing compound according to claim 3.
13. An epoxy resin curing agent comprising the phosphorus-containing compound according to claim 7.
US14/915,766 2013-10-01 2014-11-10 Phosphorus-containing compound and curing epoxy resin composition containing same Active US9738667B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2013-206637 2013-10-01
JP2013206637 2013-10-01
PCT/JP2014/073994 WO2015049965A1 (en) 2013-10-01 2014-09-10 Phosphorus-containing compound, and curable epoxy resin composition containing same

Publications (2)

Publication Number Publication Date
US20160200747A1 true US20160200747A1 (en) 2016-07-14
US9738667B2 US9738667B2 (en) 2017-08-22

Family

ID=52778561

Family Applications (1)

Application Number Title Priority Date Filing Date
US14/915,766 Active US9738667B2 (en) 2013-10-01 2014-11-10 Phosphorus-containing compound and curing epoxy resin composition containing same

Country Status (8)

Country Link
US (1) US9738667B2 (en)
EP (1) EP3053928A4 (en)
JP (1) JP6499968B2 (en)
KR (1) KR102320939B1 (en)
CN (2) CN112029073A (en)
BR (1) BR112016005231B1 (en)
TW (1) TWI623547B (en)
WO (1) WO2015049965A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180051167A1 (en) * 2015-03-23 2018-02-22 Adeka Corporation Epoxy resin composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7066268B2 (en) * 2017-08-23 2022-05-13 株式会社Adeka Flame-retardant epoxy resin composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3475536A (en) * 1967-06-01 1969-10-28 Dow Chemical Co Method for the systemic control of ectoparasites with phosphorodiamidates
US3502690A (en) * 1965-09-03 1970-03-24 Boehringer Sohn Ingelheim (bis - dimethylamino)-(3 - phenyl - 5 - amino-1,2,4-triazolo) - phosphineoxide triphenyl-chlorostannate

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1333276A (en) * 1919-10-25 1920-03-09 Thomas E Murray Seal-fastening
US1494774A (en) * 1923-05-29 1924-05-20 Eugene H Davis Cake-cutting machine
US3531550A (en) * 1965-08-12 1970-09-29 Monsanto Co Phosphorus ester amides
US3645971A (en) * 1969-03-10 1972-02-29 Hooker Chemical Corp Fire retardant epoxy resins containing phosphoramidates
US3764374A (en) * 1970-07-21 1973-10-09 Eastman Kodak Co Process for placing modifiers within polyester fibers and films
FR2102301A1 (en) * 1970-08-17 1972-04-07 Monsanto Co
BE802990A (en) * 1972-07-31 1974-01-30 Monsanto Co FIRE RETARDANTS AND THEIR PREPARATION
JPS5438649B2 (en) * 1972-11-28 1979-11-22
JPS5082150A (en) * 1973-11-21 1975-07-03
JPS5093949A (en) * 1973-12-24 1975-07-26
DD117153A3 (en) * 1974-02-12 1976-01-05
DE2505326A1 (en) * 1974-02-18 1975-08-21 Sandoz Ag FLAME RESISTANT REGENERATED CELLULOSE
US4062909A (en) * 1974-04-08 1977-12-13 Monsanto Company Phosphoroamidates
DE2417991A1 (en) * 1974-04-11 1975-10-23 Univ Moskovsk Polymer-stabilising thiophosphoric acid triamides - prepd from tetraphosphorus decasulphide and aromatic or aliphatic amines or alcohols
US4086302A (en) * 1975-07-28 1978-04-25 Monsanto Company Phosphoroamidates
US4518413A (en) * 1983-06-06 1985-05-21 Allied Corporation Poly-phosphorodiamide urease inhibitors and urease inhibited urea based fertilizer compositions
JPH08337709A (en) 1995-04-10 1996-12-24 Shin Etsu Chem Co Ltd Epoxy resin composition for semiconductor sealing and semiconductor device
JPH10195178A (en) 1997-01-06 1998-07-28 Toshiba Chem Corp Flame-retardant epoxy resin composition, prepreg, laminate and copper-clad printed circuit board
JPH10265487A (en) * 1997-03-21 1998-10-06 Kanagawa Univ Production of phosphonic acid ester and polyphosphonate and curable composition
RU2175242C1 (en) * 2000-09-27 2001-10-27 Московский НИИ глазных болезней имени Гельмгольца Method of treating uveal melanoma
CN102617637B (en) * 2012-02-23 2015-07-08 四川大学 Preparation method of organophosphorus nitrogen system flame retardant with hydroquinone phosphate ester serving as framework

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3502690A (en) * 1965-09-03 1970-03-24 Boehringer Sohn Ingelheim (bis - dimethylamino)-(3 - phenyl - 5 - amino-1,2,4-triazolo) - phosphineoxide triphenyl-chlorostannate
US3475536A (en) * 1967-06-01 1969-10-28 Dow Chemical Co Method for the systemic control of ectoparasites with phosphorodiamidates

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Hamed et al (2007): STN International HCAPLUS database, (Columbus, Ohio), Accession number: 2007:379592. *
Rittig et al (2008): STN International HCAPLUS database, (Columbus, Ohio), Accession number: 2008:252741. *
Wade et al (1970): STN International HCAPLUS database, (Columbus, Ohio), Accession number: 1970:24625. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180051167A1 (en) * 2015-03-23 2018-02-22 Adeka Corporation Epoxy resin composition
US10655005B2 (en) * 2015-03-23 2020-05-19 Adeka Corporation Epoxy resin composition

Also Published As

Publication number Publication date
EP3053928A1 (en) 2016-08-10
EP3053928A4 (en) 2017-03-01
KR102320939B1 (en) 2021-11-03
CN105764910A (en) 2016-07-13
WO2015049965A1 (en) 2015-04-09
JPWO2015049965A1 (en) 2017-03-09
JP6499968B2 (en) 2019-04-10
US9738667B2 (en) 2017-08-22
BR112016005231B1 (en) 2021-04-13
CN112029073A (en) 2020-12-04
TWI623547B (en) 2018-05-11
KR20160065814A (en) 2016-06-09
TW201518312A (en) 2015-05-16

Similar Documents

Publication Publication Date Title
WO2010113784A1 (en) Epoxy resin, epoxy resin composition, and cured object
JP6161340B2 (en) Bisimidazole compound, epoxy resin curing agent containing the bisimidazole compound, and one-component curable epoxy resin composition containing the epoxy resin curing agent
US9738667B2 (en) Phosphorus-containing compound and curing epoxy resin composition containing same
US10562924B2 (en) Phosphorus-containing compound, and curable epoxy resin composition containing same
KR102311142B1 (en) Novel compound and epoxy resin composition containing same
JP6240940B2 (en) Epoxy resin composition
JP5996977B2 (en) Polythiourethane compound, epoxy resin curing agent containing the compound, and one-part curable epoxy resin composition comprising the epoxy resin curing agent
US7074946B2 (en) Method of producing glycidyl 2-hydroxyisobutyrate
JP6307245B2 (en) Epoxy resin composition
JP4605855B2 (en) Epoxy resin composition
JP5126923B2 (en) Epoxy resin composition
JP2001181238A (en) Alicyclic group-containing ester compound and method for producing the same
JP6300608B2 (en) Novel compound and epoxy resin composition containing the same
CA2026255A1 (en) Phosphorus-containing copolymers and their use

Legal Events

Date Code Title Description
AS Assignment

Owner name: ADEKA CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ENDO, TAKESHI;MATSUMOTO, KOZO;TAMASO, KEN-ICHI;AND OTHERS;REEL/FRAME:037863/0817

Effective date: 20160203

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4